JPH08253637A - Composition and its use - Google Patents

Abstract

PURPOSE: To obtain a composition high in an antimicrobial property, excellent in a stain-preventing function, giving an inexpensive mat film not relustered when heated, and useful for producing wall paper, especially substitutes for Japanese paper requiring a gas barrier property. CONSTITUTION: A composition comprises (a) EVOH having an ethylene content of 20-65mol.% and a vinyl ester component-saponification degree of >=90mol.% (b) an inorganic filler, and (d) an inorganic oxo acid having an antimicrobial metal ion, wherein (a):(b)=(50-95wt.%):(50-5wt.%), and (d): (a)+(b)}=(0.1-10 wt.%):(99.90wt.%). A composition comprises (a) the EVOH, (b) the inorganic filler, (c) CMPE, and (d) the antimicrobial acid agent, wherein (a):(b):(c)=(40-90 wt.%):(30-5wt.%):(30-5wt.%), and (d): (a)+(b)+(c)}=(0.1-10wt.%):(99.9-90wt.%). An interior material is obtained by using this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for an inexpensive matted film material which is antibacterial and does not easily lose its matte when heated and its use.

[0002]

2. Description of the Related Art Conventionally, wallpaper containing a polyvinyl chloride resin layer is known. However, wallpaper containing these polyvinyl chloride resin layers and decorative boards used for ceiling materials, wall materials, floor materials, etc. for general households, hospitals, clinics, restaurants, factories, ships, trains, automobiles, etc. , Hand marks, graffiti,
It is easily contaminated with pigments in various foods. Also, the plasticizer for polyvinyl chloride resin bleeds on the surface of the wallpaper.
Dust adheres to the bleeding plasticizer, and the PVC wallpaper becomes more easily soiled. There is also a problem that it does not have the effect of suppressing the growth of bacteria, which prevents nosocomial infections, which is a problem in hospitals and clinics. In addition, various matt films are used as substitutes for Japanese paper in packaging of Japanese confectionery, insect repellents, soaps, etc. However, gas barrier properties are insufficient, so improvement of gas barrier properties is required.

As disclosed in JP-A-58-23973, there is known a stain resistant wallpaper in which an acrylic resin film is laminated on a vinyl chloride wallpaper. However, although these wallpapers have excellent stain resistance compared to non-laminated PVC wallpaper, they are not perfect, and there is a problem that the tendency becomes large especially when a long period of time has passed after lamination. Further, the acrylic resin film is inferior in chemical resistance and is particularly apt to be attacked by esters, ketones, aromatic compounds and the like, so that it is necessary to pay attention to wiping off stains, which is not satisfactory.

JP-A-60-135225 and JP-A-60-195129 describe a matted film in which talc is blended with an acrylic resin, but the matting effect is insufficient, and the antibacterial effect is also known. Is not stated.

As disclosed in Japanese Utility Model Publication No. 59-172797, a stain-resistant wallpaper is known in which a film of a saponified product of an ethylene-vinyl ester copolymer (hereinafter referred to as EVOH) is laminated on a vinyl chloride wallpaper. There is. This wallpaper is
It has excellent chemical resistance and plasticizer barrier properties, and is more resistant to stains than non-laminated PVC wallpaper. Furthermore E
The VOH film has a relatively small electric resistance and is less likely to be charged with static electricity, and therefore has an advantage that dust is not easily attached to the surface of the wallpaper. However, even in the above-mentioned Jitsukaisho, there is no description about the antibacterial effect.

On the other hand, Japanese Patent Application Laid-Open No. 4-173244 describes an antibacterial plastic multilayer film characterized in that the outermost layer and / or the innermost layer of the plastic multilayer film is a film layer containing an inorganic antibacterial substance. is there. However, the above-mentioned Japanese Patent Laid-Open No. Heihei does not describe the incorporation of a specific antibacterial agent into EVOH, and does not describe anything about appliances and building materials.

JP-A-60-224542 and JP-A-60-224542
In JP-A-239233, JP-A-60-242053 and JP-A-62-15265, EVOH is also excellent in blocking the plasticizer for polyvinyl chloride resin, and EVOH is a plasticizer for polyvinyl chloride resin. It is described that the contamination resistance can be improved by using it for blocking. However, even in the above-mentioned Japanese Laid-Open Patent Publication, there is no description about a matted film.

JP-B-51-21822, JP-A-61-161
No. 242841 and JP-A No. 62-143980 describe a blend of EVOH and an inorganic filler, but do not describe a stain resistance and a matted film.

JP-A-64-74252 and JP-A-1-
No. 166951 describes a laminate of a matt film made of EVOH and a carboxylic acid-modified polyethylene resin (hereinafter abbreviated as CMPE) and polyvinyl chloride. However, both EVOH and CMPE are expensive, and an inexpensive matted film is desired. Further, there is a drawback that the matte tends to return during heating for embossing.

Japanese Unexamined Patent Publication (Kokai) No. 6-263933 describes a laminate of a polyvinyl chloride and a matt film made of EVOH, a carboxylic acid-modified polyethylene resin, and an inorganic oxo acid having an antibacterial metal ion. But EV
Both OH and CMPE are expensive, and an inexpensive matted film is desired. Further, there is a drawback that the matte tends to return during heating for embossing.

[0011]

As described above, there is a strong demand for an inexpensive matte film which has antibacterial properties and antifouling functions and which is less likely to lose its matte when heated, especially interior materials such as wallpaper. ing. As a substitute for Japanese paper, a matted film having a good gas barrier property is required.

Therefore, the present invention was devised in order to solve the above-mentioned drawbacks of the prior art, and has antibacterial properties, barrier property of a plasticizer for polyvinyl chloride resin, antifouling function, etc. An object of the present invention is to obtain an inexpensive matted film which has a matte structure and is less likely to lose its matte upon heating, and a matte film which has good gas barrier properties as a substitute for wallpaper, especially wallpaper and Japanese paper.

[0013]

Means for Solving the Problems The above-mentioned object is ethylene-
Saponified vinyl ester copolymer (a) (hereinafter EVOH
,), An inorganic filler (b), and an inorganic oxo acid (d) having an antibacterial metal ion, and the composition ratio of each component is (a) :( b) = 50 to 95% by weight: 50 to 5% by weight. %, (D): {(a) + (b)} = 0.1 to 10% by weight: 99.9 to 90% by weight, or EV
OH (a), an inorganic filler (b), a carboxylic acid-modified polyethylene resin (c) (hereinafter referred to as CMPE) and an inorganic oxo acid (d) having an antibacterial metal ion,
The composition ratio of each component is (a) :( b) :( c) = 40 to 90
% By weight: 30 to 5% by weight: 30 to 5% by weight, (d):
{(A) + (b) + (c)} = 0.1 to 10% by weight: 9
It is achieved by providing a composition consisting of 9.9 to 90% by weight and a matted film using the same.
It is also achieved by providing an interior material in which the matted film is laminated on at least one surface of a base material such as a polyvinyl chloride resin layer containing a plasticizer, in particular, the outermost layer.

In the present invention, a typical example of the inorganic oxoacid salt (d) having a specific antibacterial metal ion is a metal ion of an inorganic oxoacid salt which is ion-exchanged with an antibacterial metal ion. To be Here, examples of the inorganic oxo acid salt include silicates, phosphates, titanates, antimonates, and the like, and examples of the silicates include magnesium metasilicate aluminate, calcium silicate, magnesium silicate, and phosphorus. Calcium phosphate as acid salt,
As zirconium phosphate and titanate, potassium titanate, calcium titanate, and as antimonate, compounds such as sodium antimonate are preferable.
Particularly, magnesium aluminometasilicate and apatite containing calcium phosphate as a main component are preferable from the viewpoint of safety. Apatite is also called apatite, and is a general term for fluorapatite, chlorapatite, and hydroxyapatite.

The oxo acid salt may be a preformed one or a granular one. The particle size is 2μm in order to develop the antibacterial property, especially the antibacterial property of wallpaper.
It is particularly preferable that the thickness be 0.5 μm or less.

As the metal ion having an antibacterial property to be ion-exchanged, a metal ion generally used as an antibacterial agent or a bactericide, for example, silver, copper, zinc, tin, mercury, lead, cadmium, etc. can be applied. Especially, metal ions of silver, copper, zinc, and tin are desirable in terms of safety to human body.

These metal ions are ion-exchanged with the metal ions of the oxo acid salt by a conventional method.

For example, ion exchange of silver, copper, zinc, tin, etc. is carried out in a region where the pH value is lower than the pH value for forming hydroxide and the oxo acid salt is not dissolved. That is, pH is 9 to 4 for silver, pH 6 to 4 for copper, and pH for zinc.
The temperature range is preferably in the range of 9 to 4 and 60 ° C. or higher. The proportion of the antibacterial metal ion to be ion-exchanged is appropriately 0.1 to 90 mol% of the ion-exchange capacity of the oxo acid salt, and the ion-exchanged ion in the antibacterial agent is the antibacterial agent. Is preferably 0.01 to 40% by weight. If the metal ion is less than the above-mentioned minimum value, the antibacterial property is not sufficient, and if it exceeds the maximum value, the metal ion becomes unstable and the antibacterial effect is not stable and long-lasting.

The antibacterial agent used in the present invention is different from silver zeolite (aluminosilicate hydrous alkali metal salt or alkaline earth metal salt ion exchanged with a metal ion such as silver). It is possible to use together with other antibacterial agents such as silver zeolite.

In the present invention, EVOH (a) has an ethylene content of 20 to 65 mol%, preferably 2
5-60 mol%, saponification degree of vinyl ester component is 90
A substance having a mol% or more, preferably 95 mol% or more is suitably used. If the ethylene content is less than 20 mol%, the water resistance is poor, and if it exceeds 65 mol%, the oil resistance and the gas barrier property are poor, and oily pollutants easily permeate, which is unfavorable. Even if the degree of saponification of the vinyl ester component is less than 90 mol%, the oil resistance and gas barrier properties are poor, and oily pollutants easily permeate, which is also unfavorable because the stain resistance is poor. As a vinyl ester used as a raw material for EVOH, vinyl acetate is preferable from the economical viewpoint. Comonomer components other than ethylene and vinyl ester can be used in this EVOH within a range that does not impair the object of the present invention.

EVOH may be a composition of two or more kinds of EVOH having different ethylene contents, degrees of saponification and degrees of polymerization, and boric acid, an antioxidant, and
You may blend thermoplastic resins, such as a slip agent, a coloring agent, a deodorant, polyamide, and polyolefin.

In the present invention, the inorganic filler (b) preferably has a whiteness of 80 or more as measured by reflectance with a Kett photoelectric whiteness meter, and has a weight average flake diameter of "film thickness x 0.8". It is preferable that the particle size is not more than μm. From the viewpoint of the hue of the matted film, the whiteness is preferably 80 or more, and the weight average flake diameter exceeds "film thickness × 0.8" μm, EV
The blendability with OH and the film-forming property of the matted film obtained by blending are deteriorated. That is, the weight average flake diameter depends on the film thickness, but is preferably 6 μm or less, and more preferably 4 μm or less. The lower limit value is not particularly limited. The weight average flake diameter of the above-mentioned inorganic filler was confirmed by a scanning electron microscope to be almost the same as the value of the raw material inorganic filler before being mixed with EVOH and the value of the inorganic filler present in the matte film. In the present invention, the weight average flake diameter of the inorganic filler means the weight average flake diameter of the raw inorganic filler before being mixed with EVOH or the weight average flake diameter of the inorganic filler present in the matted film. .

In the present invention, the weight average flake diameter is
The inorganic filler was classified with a microsieve or a sieve having various openings, the results were plotted on a Rosin-Rammlar diagram, and 50% of the total weight of the inorganic filler used for measurement was plotted.
Micro sieve or sieve opening through which% passes L ↓ 50
Is a value corresponding to. That is, the weight average flake diameter L of the inorganic filler is defined by the formula (I) or (II). L = L ↓ 50 (for microsieve) (I) L = 20 ↑ 1/2 * L ↓ 50 (for sieve) (II)

Here, of the inorganic filler, a large particle size portion is classified by a sieve, and a small particle size portion is classified by a microsieve. As the inorganic filler in the present invention, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, clay, kaolin, sericite, glass flakes,
Examples include viscous minerals such as mica, smectite and vermiculite. Of these, EV is talc and mica.
It is preferable in terms of uniform mixing with OH and film forming property of a matted film. These inorganic fillers may be used alone or in combination of two or more. Also, these inorganic fillers may be used as they are,
If necessary, those surface-treated with a surfactant or a silane coupling agent can be used. In the present invention, it is particularly important to add an inorganic filler, and by adding an inorganic filler, the matting effect becomes sufficient,
In addition, it becomes difficult for matte to return.

In the present invention, the carboxylic acid-modified polyethylene resin (CMPE) (c) is a polyethylene resin obtained by graft-polymerizing an α, β-unsaturated carboxylic acid or the carboxylic acid anhydride. The content of α, β-unsaturated carboxylic acid or carboxylic anhydride is 0.0005 to 0.5 mol%, preferably 0.001 to 0.5 mol%.
It is 0.4 mol%. Α, β for all polyethylene resins
-It is preferable that the unsaturated carboxylic acid or the carboxylic acid anhydride is graft-modified, but it is a blend of a high concentration carboxylic acid-modified seed polymer and an unmodified polymer, and the final graft amount is within the above range. It may be. α, β-
Examples of the unsaturated carboxylic acid or the carboxylic acid anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, with maleic anhydride being preferred. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, with high-density polyethylene being preferred. By blending CMPE, it is possible to increase the external haze without lowering the tensile elongation.

EVOH (a), inorganic filler (b) and C
The composition ratio of MPE (c) and the antibacterial agent (d) is such that the composition ratio of each component is (a) :( b) = 50 to 95% by weight: 50 to 5% by weight, (d): {(a) + (B)} = 0.1 to 10% by weight: 99.9 to 90% by weight, or (a) :( b):
(C) = 40 to 90% by weight: 30 to 5% by weight: 30 to 5
% By weight, (d): {(a) + (b) + (c)} = 0.1
10 to 10% by weight: 99.9 to 90% by weight, preferably the composition ratio of each component is (a) :( b) = 60 to 90% by weight: 40 to 10% by weight, (d): {( a) + (b)} =
0.1-10% by weight: 99.9-90% by weight, or
(A) :( b) :( c) = 50-80% by weight: 25-1
0% by weight: 25 to 10% by weight, (d): {(a) +
(B) + (c)} = 0.1-10 wt%: 99.9-9
0% by weight. When the weight of the inorganic filler exceeds the above range, pinholes are likely to occur in the matte film when deep embossing is applied, and when the weight of the inorganic filler is less than the above range, matting is insufficient. When the weight of CMPE exceeds the above range, the matted film tends to be expensive. Further, if the weight of the antibacterial agent is less than the above range, the antibacterial function is not sufficient, and if it exceeds the above range, the film is liable to be scratched and cannot be practically used.

In the present invention, EVOH, an inorganic filler, an antibacterial agent, and further, these and CMPE are melt-blended by a method of pre-blending using a twin-screw extruder, Brabender Plastograph, etc. Alternatively, a method of directly feeding to various molding machines and molding while kneading with the molding machine, once preparing high-concentration master pellets with an extruder, and melt-extruding a product diluted to about 1/1 to 1/30 There are ways to do that. In order to disperse the inorganic filler and the antibacterial agent more uniformly, a metal soap such as sodium stearate, magnesium stearate and zinc stearate, and a dispersion aid such as ethylene bis fatty acid amide and polyethylene wax may be added. Further, an antioxidant and an ultraviolet absorber may be added.
The order of blending is not particularly limited.

Further, a method of dispersing an inorganic filler, an antibacterial agent and CMPE in a solution of EVOH, or a method of dissolving EVOH in a dispersion liquid of an inorganic filler, removing the solvent and then blending with the antibacterial agent and CMPE may be used. An inorganic filler may be dispersed in a solution of an ethylene-vinyl ester copolymer, and then saponified and the solvent may be removed to obtain EVOH, which may be blended with an antibacterial agent and CMPE. When the ethylene-vinyl ester copolymer is polymerized, An inorganic filler may be dispersed.

The thickness of the matted film of the present invention is not particularly limited, but is preferably 10 to 40 μm, and 10 to 3
0 μm is more preferable. When the thickness of this composition layer is, for example, less than 10 μm when laminated with a polyvinyl chloride resin layer, pinholes are easily generated in the matte film during embossing, and the plasticizer blocking property in the polyvinyl chloride resin layer is high. Is preferable, and if it exceeds 40 μm, the cost becomes high.

In the present invention, the matte film has a surface glossiness of 50% or less, preferably 45% on at least one side.
Below, it is important that it is more preferably 40% or less. When the surface glossiness exceeds 50%, it is insufficient as a matte film. Here, the glossiness is an average value of arbitrary 5 points measured at an angle of 75 degrees with a Murakami glossiness meter.

The matted film of the present invention can be obtained by a melt extrusion method such as a T-die method or an inflation method. For example, when a film is obtained by the T-die method, rapid cooling of the extruded film is a preferable condition. Here, the rapid cooling means that the air gap of the die is made as small as possible and the air is rapidly cooled by the cast roll by the air slit. In the present invention, the composition layer (matted film layer) is effectively used as a laminate with another resin. Examples of the other resin layer include polyvinyl chloride resin, particularly polyvinyl chloride resin containing a plasticizer, polyolefin (polyethylene, polypropylene, etc.), polystyrene, polyester, polyamide and the like. The laminated body is obtained by dry laminating, heat laminating, and polysand laminating. A laminate can also be obtained by a method of extrusion laminating the composition of the present invention into another resin film, or by coextruding the composition of the present invention and another resin.

The composition and matted film of the present invention are used for interior materials, packaging materials and the like, and among them, they are particularly useful for interior materials. A typical example of the interior material is a wallpaper, and examples of the wallpaper include a composition in which the polyvinyl chloride resin layer containing a plasticizer is laminated on the composition layer of the present invention. Here, wallpaper means polyvinyl chloride resin, plasticizer, if necessary, pigment, filler, stabilizer, etc. mixed on a support made of flame-retardant paper, non-woven fabric, glass fiber, asbestos paper, etc. The composition is laminated by a calendar method, a coating method, or the like, further, a product obtained by subjecting these laminated materials to a printing process, and by adding a foaming agent, the final product is 1.5 to 15 times larger. Examples include foamed polyvinyl chloride resins. Other interior materials include decorative boards (printed decorative boards that are printed on thin paper and laminated on a support made of plywood, particle board, etc.), decorative gypsum boards, PVC steel sheets, PVC non-combustible boards, PVC decorative boards, etc. Can be given.

In the present invention, the plasticizer for polyvinyl chloride resin is liquid at 20 ° C., and is 20 to 7 relative to the total weight.
5% by weight, preferably 25 to 55% by weight. Two
As a plasticizer which is liquid at 0 ° C., dibutyl phthalate,
Di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, didecyl phthalate, dinonyl phthalate, butyllauryl phthalate,
Phthalate ester plasticizers such as dilauryl phthalate and butylbenzyl phthalate, tricresyl phosphate,
There are phosphate ester plasticizers such as tributyl phosphate and tri-2-ethylhexyl phosphate, and chlorine-containing plasticizers such as chlorinated paraffin.

In the present invention, the method for laminating the matte film is not particularly limited. Actual exploitation 59-17279
No. 7, a method using a urethane adhesive, JP-A-60-224542 and JP-A-60-239233.
As described in JP-A No. 60-242053 and JP-A-60-242053, a method of using a mixture of a modified product of a copolymer of vinyl acetate and vinyl chloride and a urethane adhesive is exemplified.
Alternatively, the composition and a thermoplastic resin capable of adhering to both polyvinyl chloride and the composition may be coextruded, and the obtained film may be laminated.

The laminate of the present invention thus obtained is
Even when used for a long period of time, it retains its anti-staining function and does not return matte upon heating, and is very useful as an interior material, especially as a wallpaper.

Another typical example of the use of the present invention is to use the composition layer of the present invention as an alternative to Japanese paper having a gas barrier property and laminate it with another resin. As described above, the laminating method includes a method of co-extruding the composition and another resin, a method of extrusion laminating the composition to another film, a method of dry laminating another film and a matted film, and a matted film. A known method such as a method of extrusion laminating another resin can be adopted. The laminate obtained in this manner is cheaper than the laminate obtained by laminating Japanese paper and a gas barrier film. Washi alternatives include Japanese sweets, bean sweets, delicacies,
Examples include food such as bonito flakes, insect repellents, and chemicals such as soap.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0038]

【Example】

Example 1 3.2 g of silver nitrate and 5.7 g of copper sulfate were dissolved in 5 l of pure water to adjust the pH to 5. In this aqueous solution, magnesium aluminometasilicate (Al ↓ 2O ↓ 3 ・ MgO ・ 2SiO)
↓ 2.7H ↓ 2O, average particle size 0.02μm, moisture content 20
125% by weight) and again adjusting the pH to 5, 6
Stirred at 0 ° C. for 1 hour. Then, it was washed with 5 equivalents of warm water, dried at 100 ° C. for 4 hours, and further baked at 600 ° C. for 2 hours to obtain an antibacterial agent.

Next, the ethylene content was 33 mol%, the saponification degree of the vinyl acetate component was 99.5 mol%, and the MI was 5.5 g / 1.
0 minutes EVOH 80 parts by weight, weight average flake diameter 1.5
20 parts by weight of talc powder having a micrometer and whiteness of 95 and 1 part by weight of the above antibacterial agent were blended and pelletized at 220 ° C. using a 30 mmφ twin screw extruder. The blended pellets were mixed with a 20 mmφ single screw extruder (extrusion temperature 220 ° C., L / D = 20) to obtain an air gap of 0.
A matted film (gloss 17%) having a thickness of 5 μm and a cast roll temperature of 60 ° C. and a thickness of 15 μm was obtained. A gravure coater is used for this film, and a urethane adhesive Adcoat AD-335A having a solid content of 20% by weight and a curing agent Ca are used.
t-10 (manufactured by Toyo Morton Co., Ltd., mixing ratio 17: 1) was coated so that the coating amount was 2 g / m ↑ 2 (based on solid content), dried at 70 ° C. for 4 minutes, and then again gravure coater. MPR-TM (manufactured by Nisshin Chemical Industry Co., Ltd.), which is a modified product of a vinyl acetate / vinyl chloride copolymer dissolved in a solid content concentration of 18% by weight, is applied at a coating amount of 2 g / m 2 (solid content). (Standard), and dried at 70 ° C. for 1 minute.

On the other hand, 100 parts by weight of paper, 100 parts by weight of polyvinyl chloride resin and 5 parts by weight of filler are added to flame-retardant paper for backing impregnated with 24 parts by weight of guanidine sulfamate flame retardant.
0 parts by weight, plasticizer (di-2-ethylhexyl phthalate) 55 parts by weight, pigment 20 parts by weight, flame retardant 3 parts by weight, stabilizer 2 parts by weight, foaming agent 2 parts by weight, and binazine (organic antibacterial agent) After laminating 2 parts by weight of the formulation, vinyl chloride was foamed to obtain a vinyl chloride wallpaper.

An adhesive surface coated on the matte film,
Combine the polyvinyl chloride resin surfaces laminated on the paper, 150 ℃
It was pressed with a hot embossing roll and simultaneously embossed to obtain a wallpaper with a stain prevention function. There was no matte return (reduction of external haze) during embossing, and a good appearance was retained.

In order to investigate the stain prevention function, E of the wallpaper
Oily red ink (Mitsubishi Marker manufactured by Mitsubishi Pencil Co., Ltd.) and soy sauce (Kikkoman dark mouth manufactured by Kikkoman Co., Ltd.) were applied to the VOH surface in a size of 2 cm × 2 cm, and wiped off with gauze with benzine after 24 hours. No trace was left on the surface, and even if wiped off with gauze moistened with a neutral detergent, no trace was left on soy sauce, and the surface was not damaged by water, and it had sufficient water resistance. It was confirmed that the stain prevention function was complete, as shown in Table 1.

To examine the antibacterial function, Escherichia coli (Esc
herichia coli) 3.0 × 10 ↑ 4 /
The above-mentioned antibacterial EVO was added to 5 ml of physiological saline having a concentration of ml.
When 1 g of H film was added and shaken at 28 ° C. for 24 hours, the number of viable cells was measured. As shown in Table 2, 1.0 × 10 ↑ 2 cells /
It was very good with ml. Separately, the antibacterial EVOH film was stored at 20 ° C. for half a year and its antibacterial function was examined.

An adhesive for dry lamination was applied to the resulting matted film {Takelac A manufactured by Takeda Pharmaceutical Co., Ltd.
-385 / Takenate A-50 mixed in a ratio of 6: 1}
3 g / m ↑ 2 as a solid content, and after evaporating the solvent at 70 ° C., a low-density polyethylene film having a thickness of 60 μm {Suzuron L S201 manufactured by Aicero Chemical Co., Ltd.}
Were laminated to obtain a laminated film.

Oxygen permeation rate is 10.0 ml / m ↑ 2 ・ 24
h • atm (Modern Controls, O
xtran 10 / 50A type was measured at 20 ° C. and 85% RH), and the gas barrier property was good (Table 3).

Comparative Example 1 The procedure of Example 1 was repeated except that the antibacterial agent was not added. A film was obtained from the blended pellets, and the stain prevention function and antibacterial function were tested in the same manner as in Example 1. The results are shown in Table 1 and Table 2, respectively, but the stain preventing function was complete, but the antibacterial function was not present.

Comparative Example 2 The procedure of Example 1 was repeated except that the EVOH was changed to 50 parts by weight and the talc was changed to 50 parts by weight. However, good film formation was not possible due to perforation, and the subsequent evaluation was interrupted. did.

Comparative Example 3 The procedure of Example 1 was repeated except that polyethylene was used instead of EVOH, and the stain prevention function and antibacterial function were similarly tested. The results are shown in Table 1 and Table 2, respectively, but the antifouling function is incomplete and the antibacterial function is also present.
It was inferior to the VOH type.

Comparative Example 4 The procedure of Example 1 was repeated except that the talc powder having a weight-average flake diameter of 12 μm and a whiteness of 95 was used, but pinholes were too frequent to form a good film. The subsequent evaluation was interrupted.

Comparative Example 5 The procedure of Example 1 was repeated except that talc was not added. A film was obtained from the blended pellets, and the stain prevention function and antibacterial function were tested in the same manner as in Example 1. The results are shown in Table 1, Table 2 and Table 3, respectively. Although the stain preventing function and the antibacterial function were perfect, the glossiness was 95% or more and there was no matte property.

Example 2 The procedure of Example 1 was repeated except that the amount of EVOH was changed to 70 parts by weight, talc 15 parts by weight, CMPE 15 parts by weight, and antibacterial agent 1 part by weight. The matte film had a gloss of 22%, and as shown in Table 1, the stain prevention function was perfect. Oxygen permeation rate is 13.0 ml / m ↑ 2
-It was 24h-atm, and the antibacterial function was sufficient.

Comparative Example 6 In Example 2, 35 parts by weight of EV0H and 50 parts of CMPE were used.
The procedure of Example 2 was repeated except that the weight part was changed. The matte film had a gloss of 15%, and as shown in Table 1, the stain prevention function was incomplete. The oxygen transmission rate is 1
It was inferior at 00.0ml / m ↑ 2 ・ 24h ・ atm.

Comparative Example 7 The procedure of Example 2 was repeated except that EV0H was 70 parts by weight, talc was 0 parts by weight, and CMPE was 30 parts by weight. The glossiness of the matte film was 24%, and as shown in Table 1, the antifouling function was perfect. In addition, the amount of oxygen permeation is 38.0 ml / m ↑ 2 ・ 24h ・ at
The antibacterial function was sufficient as shown in Table 2. In addition, during embossing, the matte return was large.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

EFFECTS OF THE INVENTION A cheap matte film and laminate having high antibacterial properties, excellent antifouling function, and matting property when heated are obtained. It is useful as a substitute for.

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Claims (4)

[Claims] 1. An ethylene-vinyl ester copolymer saponified product (a) having an ethylene content of 20 to 65 mol% and a saponification degree of a vinyl ester component of 90 mol% or more, an inorganic filler (b) and an antibacterial metal ion. The composition ratio of each component is (a) :( b) = 5.
0 to 95% by weight: 50 to 5% by weight, (d): {(a) +
(B)} = 0.1 to 10% by weight: 99.9 to 90% by weight
Is a composition. 2. An ethylene-vinyl ester copolymer saponified product (a) having an ethylene content of 20 to 65 mol% and a saponification degree of a vinyl ester component of 90 mol% or more, an inorganic filler (b), a carboxylic acid-modified polyethylene resin ( c) and an inorganic oxo acid (d) having an antibacterial metal ion, and the composition ratio of each component is (a) :( b) :( c) = 40 to
90% by weight: 30 to 5% by weight: 30 to 5% by weight,
(D): {(a) + (b) + (c)} = 0.1 to 10% by weight: 99.9 to 90% by weight. 3. A composition according to claim 1 or 2,
A matte film having a surface glossiness of 50% or less on at least one side. 4. An interior material having the composition layer according to claim 1 or 2 on at least one surface of a polyvinyl chloride resin layer containing a plasticizer.